JPH02107616A - Blocked polyisocyanate dispersion - Google Patents

Abstract

PURPOSE:To obtain the title dispersion good in storage stability with its foaming suppressed, suitable as a coating etc., by dispersing in an aqueous medium as the main component a plurality of each specific component such as a polyacrylic alkyl ester partially hydrolyzed ammonium. CONSTITUTION:The objective dispersion can be obtained by dispersing in an aqueous medium as the main component (A) a compound of the formula (x is 10-60; y is 10-60; n is 1-3) [e.g. di(polyoxyethylene monostyrylphenyl)methane], (B) at least one kind of compound selected from alkylnaphthalenesulfonic acid alkali metal salts, dialkylsulfosuccinic acid alkali metal salts, alkylphenyl ethylene oxide adducts and higher alcohol ethylene oxide adducts, (C) polyacrylic alkyl ester partially hydrolyzed ammonium, and (D) a blocked polyisocyanate compound blocked with active hydrogen-contg. compound.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a polyisocyanate compound blocked with a compound having active hydrogen (hereinafter abbreviated as blocked polyisocyanate compound) useful as a paint, adhesive, varnish, etc. It is related to.

[Prior Art] Various blocked polyisocyanate dispersions have been used in the past. These blocked polyisocyanate dispersions are produced by processing blocked polyisocyanate compounds in which the isocyanate groups of various polyisocyanate compounds are blocked with a compound having active hydrogen in the presence of a surfactant using a ball mill, various media dispersers, homogenizers, etc. For example, in Example 1 of JP-A No. 57-56584, 4
．． A method of dispersing a phenol block of 4-1 diphenylmethane diisocyanate in water using a ball mill in the presence of dioctyl sulfosuccinate Na salt as a surfactant, and Example 1 of JP-A-55-152815 discloses , ε-caprolactam block of polymethylene polyphenylisocyanate, methyl cellulose,
A method is disclosed in which sodium alkyl sulfonate and polyethylene glycol monolaurylate are dispersed in water using a ball mill.

[Problems to be Solved by the Invention] When these blocked polyisocyanate dispersions are left for a long period of time, the blocked polyisocyanate compound separates from the water and settles and sticks to the bottom of the container, making it difficult to use. There was a problem. Blocked polyisocyanate dispersion liquids can also be used during stirring and fabrication when diluted with water or mixed with other aqueous liquids, such as epoxy compound aqueous solutions, polyester aqueous solutions, rubber latex, resorcinol/formaldehyde resin aqueous solutions, etc. Since it foams violently during the squeezing process after it is applied to knitted fabrics, etc., there are problems such as reduced operability and the necessity of using an antifoaming agent.

[Means for Solving the Problems] The object of the present invention described above is to provide a compound represented by A, the following general formula (formula) (however, the above CI), in which X is an integer of 10 to 60, and y is O to 60 integers, n represents an integer of 1 to 3) At least 1 selected from 81 orders (a) to (d)
(a) alkali metal salt of alkylnaphthalene sulfonic acid (b) alkali metal salt of dialkyl sulfosuccinic acid (C) ethylene oxide adduct of alkylphenol (d) ethylene oxide adduct of higher alcohol C, polyacrylic acid alkyl ester partially hydrolyzed ammonium, and a blocked polyisocyanate compound blocked with a compound having active hydrogen, and the main component of the medium is water.

The compound represented by the above-mentioned formula [■] of the present invention is:
For example, di(polyoxyethylene monostyrylphenyl)methane (X in formula (I) = 10 to 60), di(polyoxyethylene distyrylphenyl)methane (formula (I)
X=10-60), di(polyoxyethylene tristyrylphenyl>methane (X-10-6 in formula (I)
0), di(polyoxyethylene polyoxypropylene monostyrylphenyl)methane (X = 1 in formula (I)
0-60. y=o~60), di(polyoxyethylene・
Polyoxypropylene distyrylphenyl) methane (
(Formula%Formula%) (x= in formula (I)
10-60. y=o~60), etc. These compounds can be used alone or in combination, but among these compounds, X-13 in formula [■]
~40. Compounds where y=0 to 10 are preferred. CI above)
The concentration of the compound represented by the formula in a medium mainly composed of water is usually adjusted to a range of 0.2 to 10% by weight. The above CI
) To dissolve the compound represented by the formula in water, the above CI
) Formula compound may be added to water and stirred, but 30 to 60
It can also be dissolved by heating to °C.

Examples of the compounds (A) to (D) of the present invention include sodium propylnaphthalene sulfonate, sodium ethylnaphthalene sulfonate, sodium dimethylsulfosuccinate, sodium diethylsulfosuccinate, and ethylene oxide (hereinafter referred to as EO) addition of octylphenol. Examples include EO adducts of lauryl alcohol (EO = 3 to 30 moles added) and lauryl alcohol (EO = 3 to 30 moles added). These compounds can be used alone or in combination. The concentration of these compounds in a medium mainly composed of water is usually 0.1 to 3% by weight.
is adjusted to the range of These compounds are added to water, stirred and dissolved.

The partially hydrolyzed ammonium of polyacrylic acid alkyl ester of the present invention is obtained by partially hydrolyzing and ammoniumizing polyacrylic acid alkyl ester with a degree of polymerization of 300 to 20,000, such as polymethyl acrylate, polyethyl acrylate, polyacrylate, etc. Examples include partially hydrolyzed and ammonium-formed butyl acrylate, propyl polyacrylate, and the like. The concentration of the partially hydrolyzed ammonium of the above-mentioned polyacrylic acid alkyl ester in a medium mainly composed of water is usually adjusted to 0.1 to 3.0% by weight. The above partially hydrolyzed ammonium of polyacrylic acid alkyl ester may be added as is or may be made into an aqueous solution in advance, and after adding a predetermined amount to water to the above concentration, it is stirred and dissolved. Moreover, partially hydrolyzed ammonium of polyacrylic acid alkyl ester can be added at any stage of the emulsification process.

The blocked polyisocyanate compound of the present invention is -
It is a reaction product of a polyisocyanate compound having two or more isocyanate groups in the molecule and a compound having an active hydrogen atom in the molecule, and specific examples include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2. 4-thalolphenylene diisocyanate, 4.4
゛-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, ω.

Diisocyanate necks such as ω-(ditrimethylenethioether) diisocyanate, S-triazine triisocyanate, thiophosphoric acid tris(p-incyanate phenyl) ester, triphenylmethane triisocyanate, diphenylmethane triisocyanate, butane-
1゜2.2-triisocyanate, trimethylolpropane tolylene diisocyanate teradduct, 2.4.1
- Triisocyanates such as diphenyl ether triisocyanate, polyisocyanate compounds such as polymethylene polyphenylisocyanate (including crude diphenylmethane diisocyanate), phenols such as phenol, cresol, thiophenol, and lactams such as ε-caprolactam and valerolactam. oxime compounds such as acetoxime, methyl ethyl ketoxime, and reactants with ethyleneimine. The concentration of these blocked polyisocyanate compounds in the dispersion is usually 10 to 50% by weight.The blocked polyisocyanate compounds are pulverized as necessary, and water is the main component. The blocked polyisocyanate dispersion of the present invention can be obtained by adding it to a medium and emulsifying it using a known fine dispersion method, for example, a ball mill, a homogenizer, various media dispersers, etc. Most of the particle diameters of the fine particles made of the blocked polyisocyanate compound in the blocked polyisocyanate dispersion are 10 μm or less, and the average particle diameter is 0.
．． It is preferably in the range of 1 to 5.0 μm.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, each evaluation in Examples was performed by the following method.

(1) Phase separation after standing The niblocked polyisocyanate dispersion was placed in a test tube with an inner diameter of 16 mm and a length of 150 mm to a depth of 100 mm, sealed with a silicone rubber stopper, and left to stand for 2 months. The liquid depth of the transparent separation layer formed above the liquid phase is expressed by a dot, and the smaller the value, the better the storage stability.

(2) Thickness of fixed sediment after standing: Gently remove the blocked polyisocyanate dispersion liquid from the test tube after evaluating the phase separation after standing in the previous section (1), and deposit/fixed sediment layer at the bottom of the test tube. The thickness of the deposit is expressed by a fence, and the smaller the value, the better the storage stability.

3) Foaming amount Niblocked polyisocyanate dispersion liquid 4
Put 5ml into a 100ml graduated cylinder, and introduce air from the bottom of the graduated cylinder through a bubble-generating glass tube (inner diameter 6mm, outer diameter 8mm, with a glass filter at the tip) at 40mm/min for 3 minutes. Check the amount of bubbles. Volume (ml
), and the smaller the value, the less bubbles are generated and the better.

Example 1. Comparative Examples 1 to 3 Di(polyoxyethylene/polyoxypropylene/tristyrylphenyl)methane (x=18.y in formula (I)
= 18 parts by weight of 3), 2 parts by weight of sodium dimethylsulfosuccinate, and 200 parts of methyl ethyl ketoxime block of 4゜4-diphenylmethane diisocyanate.
Place 742.5 parts by weight of water in a ball mill,
After treatment at 0 rpm for 36 hours, 28.5 parts by weight of a partially hydrolyzed ammonium (polymerization degree 3000) aqueous solution of butyl polyacrylate (20% by weight, 1%) was added to 760 parts by weight of the liquid extracted from the ball mill, and the mixture was stirred for 1 hour. Table 1 shows the storage stability (phase separation after standing and thickness of fixed sediment after standing) and foam height of the blocked polyisocyanate dispersion. For comparison, di(polyoxyethylene/polyoxypropylene/tristyrylphenyl)methane (
x = 18, y = 3> in formula (I), and the partially hydrolyzed ammonium aqueous solution of butyl polyacrylate is not added, and the amount of sodium dimethylsulfosuccinate added is 20 parts by weight,
The same blocked polyisocyanate dispersion as in Example 1 except that the amount of water was changed to 780 parts by weight (Comparative Example 1)
) and di(polyoxyethylene/polyoxypropylene/tristyrylphenyl)methane (x=18.
The same blocked polyisocyanate dispersion as in Example 1 (Comparative Example 2) except that y = 3) was not added, and the same as in Example 1 except that ammonium partially hydrolyzed of butyl polyacrylate was not added. The evaluation results of the blocked polyisocyanate dispersion (Comparative Example 3) are shown in Table 1.

Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 2 Di(polyoxyethylene polyoxypropylene tristyrylphenyl)methane in Example 1 (x in the formula
=18. Implemented except that di(polyoxyethylene tristyrylphenyl)methane (x = 28 in the formula) was used instead of y = 3), and sodium propylnaphthalene sulfonate was used instead of sodium dimethylsulfosuccinate. The evaluation results of the same blocked polyisocyanate dispersion as in Example 1 are shown in Table 1. Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 3 The same blocked polyamide as in Example 2 was used, except that partially hydrolyzed ammonium of polymethyl acrylate (degree of polymerization 3000) was used instead of partially hydrolyzed ammonium of butyl polyacrylate in Example 1. The evaluation results of the isocyanate dispersions are shown in Table 1. Table 1 shows that the blocked polyincyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 4 Di(polyoxyethylene polyoxypropylene tristyrylphenyl)methane in Example 1 (x in the formula
=18. The same blocked procedure as in Example 1 was used, except that di(polyoxyethylene polyoxypropylene monostyrylphenyl)methane (X = -18, y = 3 in the formula) was used instead of y = 3). The evaluation results of the polyisocyanate dispersion are shown in Table 1. From Table 1, the blocked polyisocyanate dispersion of the present invention has excellent storage stability;
It can be seen that there is little foaming.

Example 5.6 The use of an EO adduct of octylphenol (EO = 15 mole addition) in place of sodium dimethylsulfosuccinate in Example 1 (Example 5), an E○ adduct of octyl alcohol (EO = 15 mole addition). Table 1 shows the evaluation results of the same blocked polyisocyanate dispersion as in Example 1, except that the same method as in Example 1 was used (Example 6).

Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 7.8 The methyl ethyl ketoxime block of 4,4-diphenylmethane diisocyanate in Example 1 was
Replacement of 4--diphenylmethane diisocyanate with ε-caprolactam block (Example?), 4.4
--Example 1 except that diphenylmethane diisocyanate was replaced with an ethyleneimine block (Example 8)
The evaluation results of the same blocked polyisocyanate compound emulsion are shown in Table 1. Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Foaming in the squeezing step after application in Table 1 is suppressed, and antifoaming agents are unnecessary, making it excellent for use in paints, adhesives, varnishes, etc.

Claims (1)

[Claims] A. Compounds represented by the following general formula [I] and ▲numerical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] (However, x in the above [I] formula is an integer of 10 to 60, y
is an integer of 0 to 60 (7), n is an integer of 1 to 3) B, at least one selected from the following (a) to (d)
(a) alkali metal salt of alkylnaphthalene sulfonic acid (b) alkali metal salt of dialkyl sulfosuccinic acid (c) ethylene oxide adduct of alkylphenol (d) ethylene oxide adduct of higher alcohol C, polyacrylic acid alkyl ester and D, a blocked polyisocyanate compound blocked with a compound having active hydrogen, wherein the main component of the medium is water.